Process for preparing capillary active substances



Patented May 1, 1945 UNITED STATES PATIENT OFFICE PROCESS FOR PREPARING CAPILLABY ACTIVE SUBSTANCES Wintrld Hentrieh, Rodleben, near Deccan- Rosslau, and Erik Schimn and Heinz-Joachim Engelbrecht, Dessau, Germany; vested in the Alien Property Custodian No Drawing. Application March'26, 1941, Serial No. 385,298. In Germany February 23, 1940 15 Claims. (01. 260-401) This invention relates'to capillary active substances and to a process for their preparation.

- More particularly it relates to a process for-Draparing capillary active substances from sulfimides which have besides the imide group at least one group havingat least one easily exchangeable hydrogen atom or metal atom respectively linked to a hetero atom or a hetero atom group'an'dcompounds, which have in the molecule'beside's a lipophile group an easily exchangeable halogen atom.

It is an object of this. invention to provide the soap, laundry, textile, leather, fur, paper and the like industries with capillary active substances soap like salts and have excellent foaming,'wash-' ing and cleaning properties.

' In the co-pendingapplication of Winfrid Hentrich and Erik Schirm filed August 3, 1939, Ser.- No. 288,130, new Patent rid-2,292,997, there is described a process for preparing capillary active substances constituted according to the general formula R-SOzN(Kat) SO2R', wherein at least one of the two substituents R and R stands for; an organic radical containing at least one lipophile group, which may be interrupted by hetero atoms or hetero atom groups, whereas the other radical may be any hydrocarbon radical eventually interrupted by hetero atoms or hetero atom groups, and Kat denotes any desirable cation which is capable of forming water soluble salts. The process consists in condensingsulfonic acid ,halogenides of the general formula R-SO2-Hal with sulfonic acid amides of the general formula R,SO2NH2 or its suitable metal derivatives respectively and in converting the obtained condensation products with inor-f ga'nic or organic bases into water soluble salts.

In accordancewith the present invention it has been found. that in cases, where the lipophile groups of the above denoted compounds are inwhich are readily convertible into water soluble ganic sulfohalogenides and organic sulfamides or their metal compounds respectively or ammonia are condensed in accordance with known practice to'iorm sulfimides. The sulfohalogenides the groups having easily exchangeablehydrogen atoms are produced after the sulflmide condensation is performed.

According to the first step of the process e. g. the following sulfimides may be obtained m-hydroxy-dibenzene-sulfimide, p-mercaptc ethanebenzene-sulfimide, p-mercapto-dibenzene sulfimide, m-amino-benzene p' toluene sulfimide, m,m-diamino-dibenzene-sulfimide, the di-scdium salt of the methane-benzene-sulfimide-3 sulphonic acid, the 3-sulfamido-4,4'-dimethyl-dibenzene-sulfimide and the like.

As lipophile compounds having an easily exchangeable halogen atom in the molecule the following compounds may be named halogenalkyls such as butylchloride, hexylchloride, dodecylchlm.

ride, oleylchloride and the like, halogenides of fatty acids or naphthenic acids respectively such as butyric acid chloride, capronic acid chloride, capyrlic acid chloride, capric acid chloride, mixtures of fatty acid chlorides or mixtures of paraffin carboxylic acid chlorides and th like, chloro carbonic acid esters of higher molecul r aliphatic terrupted by hetero atoms or hetero atom groups, j

the synthesising of these groups is performed preferably after forming the sulflmide group First those s'ulfiinide's are prepared which contain besides the imide group at least one group having at least one easily exchangeable hydrogen atom linked to a hetero atom or a hetero atom group, which in suitable cases may also be rep-- resented by a metal atom, and hereupon these sulflmides are condensed -with compounds, having besides a lipophile group an easily'exchangeable halogen atom.

According the first stepof this process oror cycloaliphatic hydroxyl compounds as chloro carbonic acid butyl, -hexyl, -octyl, -dodecy1,

-'cyclohexyl,' methylcyclohexyl esters, 'haloge n'ides of higher molecular alkyl sulfonic acids or alkyl ar'yl sulfonic acids as hexyl-, octy1-, dodecyl sulfochlorid'es or bromides, sec.-octylbenzene sulfochloride,- sec.-dcdecylbenzene sulfochloride, the resultant products of S02 and Ch on aliphatic and aliphatic-aromatic hydrocarbons and -the like, alkylatedheterocyclic halogen compounds such as octylamino-, dodecyl-aminoor octadecylamino-cyanuric dichloride and the like and other known compoundspt these classes.

The sulfimides obtained according to the first tatelmay be indicated as follows:

step or the instant process are condensed with. the above denoted compounds with easily exchangeable halogen aton'is, if necessary in the presence of an acid binding agent such as inorganic or organic bases or alkaline reacting inorganic salts respectively e; g. soda. soda lye, sodium acetate, calcium carbonate, pyridine and the like, preferably in the presence an organic solvent such acetone, butanol, benzene, toluene or in' the sence of water.

Example 1 343 parts by weight of di-sodium salt of the methane-benzene-sulflmide-3-sultonic acid (obtained by condensation of m-nitrobenzene-suliochloride with methane -suli'amide, reduction of the nitro group to the amino group, diazotizing and conversion of the diaz'ocompound with suliurous acid), 260 parts by weight 0! cetyl chloride, parts by weight of sodium iodide and 2000 parts by weight of butanol are boiled under redevelopment of the acid begins to cease. Finally 2000 parts of water. This solution is cooled down to 2 C., whereupon at 2-5 0. 425 parts by weight of octane suli'ochloride diluted with the same volume of acetone are dropped in while vigorously stirring. Then the mixture is neutralized by a careful addition of soda lye while gradually raising the temperature'as soon as the the reaction is made up at 90 to 95 C. to constantly slight litmus allraline. Now the solution is neutralized with hydrochloric acid, then cooled down to room-temperature, whereupon the chief amount of the formed condensation product of the formula is filtered on. A little remainder maybe obtained from the filtrate by saturating with sodium chlo.

flux till the conversion is accomplished, which requires about 12 to 16 hours. The solvent is distilled off, the residue is extracted .with ben- ,zine to eliminate any residue of cetyl chloride that may still be present and is recrystallized from water or from aqueous alcohol. One ob- .tains in an output of approximately 90% a colorless powder of a good washing power which is soluble in warm water while foaming. The constitution formula of the compound is omw-sorosoi rsmwsoi-om Example 2 250 parts by weight of m'-aminoben'zene,-methane-suliimide, obtained as per Example 1 are dissolved in 1250.parts by weight 01' water underan addition of 40 parts by weight of sodium hydroxide. To this solution 200 parts by weight 01' a crystallised sodium acetate are added and the solution is cooled down to 2 C'. Now at 2 to 5 .218 parts by weight of lauric acid chloride dilutedwithin about one hour, whereupon one continues with stirring for a further hour while cooling with ride. After dryin and pulverizing a reddish powder is obtained which easily dissolves in water while foaming. This solution shows a good wetting efiect.

. Example 4 In a closed vessel with a stirring gear and a descending cooler 28 parts by weight of s-mercapto-ethane-benzene-sulflmide, obtained by the condensation of benzene-suliochloride and pi chloroethane suli'amide and conversion oi. the

condensation product with alkali hydrosuliide, are dissolved in 100 parts of water under an addition of 8 parts by weight of sodium hydroxide. Intothis solution at room-temperature a solution of 17 parts by weight of n-dodecyl-amino-cyanuric-dichloride in parts by volume of acetone is stirred in and'after a further stirring for 40 half an hour the temperature is slowly raised till with the same volume of acetone are stirred'in ice. Then one neutralizes the mixture at roomtemperature with soda and warms up to -95 (2., whereat the liquid is maintained neutral to slightly litmus'alkaline if necessary by an addition oi-i'urther amounts oi-soda. As soon as at 90 to 9; clearsolution is obtained, 175 parts by weight of. sodium chloride are added and the.

mixture is cooled down to room-temperature. It

results .a precipitate which consists of the m'-lauroylaminobenzene-methane-sulnmide and -which isiiltered and dried. The outputis nearly quan titative. Thestructural formula of the procipb.

O 'quHn w Example-i 350 parts by weight oif the sodium salt oi-the m,m-diamino-dibenzene-suliimide, obtained by the condensation'oi' 2 mols ot'm-nitrobenzenesulfochloride and 1 mol of ammonia andby the rfij 're duc-tion Qr'the nitro group, are dissolved the acetone begins to boil. distills on, is replaced by the same volume of water. Finally the mixture is warmed up to 90- 0. till no further mercapto compound is to room-temperature. The condensation product which is separated in an amorphous state having the structure formula I is now filtered oil and dried. It in hot water while foaming.

is f Examples.

To a solution oi 131 parts byiweight of ardiamino-dibensene sulflmide (obtained iby con- .9 ride and one moi oi ammonia and byredueins 'densing oi two mols oi 3 -nitrobenlsene-milio'chlo- The acetone. which present, whereupon 50 parts by weight at sodium chloride are added and the mixture is cooled down dissolves the nitro group in the obtained condensation 1 product), 53

parts by weight of sodium hydroxide and 700 parts by weight 01' water are added" gradually'at 0-2 C. while stirring 135 parts by- I weight of .caprylic acid chloride, which is dissolved in 100 parts by weight of benzene. 'lhe mixture is stirred for an hour while cooling with ice after that the temperature is raised'to roomjaemperature and finally to 50-80 0., whereupon ooled down and 50- parts by weight of conceniornieti precipitation is sucked oil.

from methanol and Walt 100'. One obtains the benzene is .distilled oil. The mixture is now c v trated hy rochloride acid areadded. The thus.

recrystallized aavaosa the fifi di- (capryloyl-aminobenaene) dlsulfimide which forms a white crystalline mass and which is converted intothe corresponding water soluble sodium salt by a treatment with soda lye. The aqueous solution of this salt possesses distinguished foaming and washing properties. The structural formula of the sodium salt may be indicated as follows:

C'iHmC ONHUSOrITJ -BOGNHO C 01H" NB Example 5- To a suspension oi. 33 parts by weight of 3,3- diamino-dibenzene-sulfimlde, 30 parts by weight of pyridine and 200 parts by weight of toluene while stirring at Ill- C. drop by drop 42 parts by weight of an organic acid chloride mixture are added, which is obtained by chlorinating a .fraotion of carboxyllc acids (B. P.n=125-160,

average molecular weight 158) produced by oxidizing paraffin. The mixture is stirred for some time at room temperature and is finally warmed, up to 70.

After cooling down and separating the tolueneby decanting, the precipitated mass is dissolved in a small amount of alcohol. To the alcoholicsolution .water is added and the mixture is made weakly alkaline by the addition of soda lye. The thus formed solution is evaporated in vacuo to dryness. One obtains a slight brownish powder in a nearlyquantitative output, which is clearly soluble in water and which shows the same properties as the product of Example 5.

We claim:

1. As a new capillary active substance a water soluble salt of the condensation product of an amino substituted dlslllfim ide and an organic acid halide having a lipophile hydrocarbon radical.

2. As a new capillary active substance the water soluble salt of the condensation product of a di(aminobenzenesu1f)'-imide and a carboxylic acid chloride containing a lipophile hydrocarbon radical.

3. As a new capillary active substance a water soluble salt of the condensation product of di(3- aminobenzene'sulf) -imide and a hlgher'fatty acidchloride.

4. As a new capillary active substance awater soluble salt of the condensation product of di(3- aminobenzenesulf) -imide and a mixture of fatty acid chlorides having 7-9 carbon atoms in the molecule. i

5. As a new capillary active substance a water soluble salt of the condensation product of di(3- aminobenzenesulf) -lmide and caprylic acid chloride.

6. As a new capillary active substance 81 water soluble salt of the condensation product of di(3- aminobenzenesulf) -imlde and a sultonlc' acid ical.

j" sull)-imide. l

Ill

8. As a new'capillary active substance th con densation product of a 'disulfimide containing in the molecule in addition to the imlde group at least one group having an easily exchangeable hydrogen atom and an organic compound having a lipophile group and a reactive halogen atom.

9. As a new capillary active substance the water soluble salt of the condensation product of a disulfimide containing in the molecule in addition to the imide group at least one group having an easily exchangeable hydrogen atom and .an organic compound having a llpophile group and a reactive halogen atom,

10. A process for preparing. a capillary-active compound which comprises producing a disulflmide having in addition to the lmide group a group containing an easily exchangeable atom selected from hydrogen and an alkaline reacting metal and then condensing said sulfimide with a compound containing a lipophile group and a reactive halogen-atom.

11. A process for preparing a capillary-active compound which comprises'produclng a disulfimide having in addition to the imidegroup a group containing an easily exchangeable atom selected from hydrogen and an alkaline reacting metal, condensing said disulfimide with a compound contalning a lipophile group and a rear:- tive halogen atom, and further reacting with a basic material to form a water-soluble salt of the dlsulfimlden 12. A process for preparing a capillary-active compound which comprises condensing an organic sulfohalide containing an easily exchangeablehydrogen atom with an organic sulfamides to form a disulfimlde, and then condensing said disulfimide with a compound containing alipophile group and a reactive halogen atom.

13. A process for preparing a capillary-active compound which comprises condensing an organic sulfohalide and an organic'sulfamide containing an easily exchangeable hydrogen atom in addition-to the sultamlde hydrogen atoms to form a disulfimide, and further condensing said disulfimide with a compound containing a lipophile group and a reactive halogen atom.

14. A process for producing a capillary-active compound which comprises condensing a disulfimide containing a readily replaceable hydrogen atom in addition to the imid hydrogen atom with a compound containing a lipophile hydrochloride containing a lipophile hydrocarbon radcarbon group and a reactive halogen atom.

- 15. A new compound, the condensation product'of a disulflmlde containing a group having an easily exchangeable hydrogen atom in addition to the imide group with an organic compound havlng a. lipophile hydrocarbon radical and a. reactive halogen atom.

wmr'nm HEN'I'RICH.

ERIK SCHIRM. rmmz-JoAcmM mamnncnr. 

